Triazine precondensate and method for obtaining the same
10941123 · 2021-03-09
Assignee
Inventors
Cpc classification
International classification
Abstract
The present invention relates to a triazine precondensate according to the general formula (I) where R.sub.1 means Q.sup.1 or a moiety of the formula R.sub.3NR.sub.4 connected with the nitrogen atom to the triazine ring of the structure of formula (I), where R.sub.9 means Q.sup.1 or a moiety of the formula R.sub.7NR.sub.8 connected with the nitrogen atom to the triazine ring of the structure of formula (I), where R.sub.2, R.sub.3, R.sub.4 and R.sub.6 mean independently from each other H, Q.sup.1 or (i), R.sub.7 and R.sub.8 mean independently from each other H, Q.sup.1, (ii) or (iii) or (i), R.sub.10 and R.sub.11 mean independently from each other R.sub.7 or R.sub.8; R.sub.5 means linear or branched C.sub.2-C.sub.20-alkyl that can be interrupted by one or more oxygen atoms, sulphur atoms, substituted or non-substituted nitrogen atoms.
Claims
1. A triazine precondensate according to the general formula (I) ##STR00035## wherein R.sub.1 means Q.sup.1 or a moiety of the formula R.sub.3NR.sub.4 connected with the nitrogen atom to the triazine ring of the structure of formula (I), R.sub.9 means Q.sup.1 or a moiety of the formula R.sub.7NR.sub.8 connected with the nitrogen atom to the triazine ring of the structure of formula (I), R.sub.2, R.sub.3, R.sub.4 and R.sub.6 mean independently from each other H or ##STR00036## R.sub.7 and R.sub.8 mean independently from each other H, ##STR00037## wherein at least one of R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7 and R.sub.8 is a C.sub.4-C.sub.6 alkyl comprising at least one OH substituent, with the proviso that when n=0, R.sub.5 is not C.sub.2H.sub.4, R.sub.10 and R.sub.11 mean independently from each other R.sub.7 or R.sub.8; R.sub.5 means linear or branched C.sub.2-C.sub.20-alkyl that can be interrupted by one or more oxygen atoms, sulphur atoms, and/or nitrogen atoms R.sub.x, R.sub.y mean independently from each other H, OH, Q.sup.1, [C.sub.1-C.sub.18]OH or ##STR00038## wherein Q.sup.1 means linear or branched C.sub.1-C.sub.12-alkyl, linear or branched C.sub.2-C.sub.12 alkenyl, C.sub.3-C.sub.7-cycloalkyl, or C.sub.6-C.sub.12 aryl; and wherein n=0-10; m=0-8; or mixtures thereof.
2. The triazine precondensate according to claim 1, wherein Q.sup.1 is a linear or branched C.sub.1-C.sub.6 alkyl.
3. The triazine precondensate according to claim 1, wherein the moiety R.sub.5 is a linear or branched C.sub.2-C.sub.10 alkyl, and the moieties R.sub.X, R.sub.y are H, OH, linear or branched C.sub.1-C.sub.10 alkyl, or linear or branched [C.sub.1-C.sub.10]OH.
4. The triazine precondensate according to claim 1, wherein the moieties R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7 and R.sub.8 are in each case H and R.sub.5 is a C.sub.2-C.sub.6 alkyl.
5. The triazine precondensate according to claim 1, comprising a melting range between 50 and 300 C.
6. The triazine precondensate according to claim 1, wherein n=1-5.
7. The triazine precondensate according to claim 1, wherein m=1-5.
8. The triazine precondensate according to claim 2, wherein Q.sup.1 is a C.sub.2, C.sub.3, or C.sub.4 alkyl.
9. The triazine precondensate according to claim 3, wherein the moiety R.sub.5 is a C.sub.3-C.sub.6 alkyl.
10. The triazine precondensate according to claim 3, wherein the moieties R.sub.X, R.sub.y are H, OH, linear or branched C.sub.2-C.sub.6 alkyl, or linear or branched [C.sub.2-C.sub.6]OH.
11. The triazine precondensate according to claim 1, wherein the precondensate comprises three or four triazine rings.
12. The triazine precondensate according to claim 1, wherein the moiety R.sub.5 is a linear or branched C.sub.3-C.sub.6 alkyl.
Description
DESCRIPTION OF THE INVENTION
(1) The invention is explained in more detail by means of the following examples.
Example 1: Comparative Example
(2) 2.5 g melamine, 105 g 1.4 butanediol and 0.5 g Ru/Al.sub.2O.sub.3 catalyst were mixed in a beaker and filled into the autoclave. The autoclave was closed and the stirrer was turned on with 500 rpm. After flushing with helium, hydrogen was flushed through the autoclave and then it was closed with atmospheric pressure of hydrogen inside. The reaction mixture was heated up to 250 C. and held at this temperature for 6 hours. After cooling down to room temperature and flushing with helium the autoclave was opened and the reaction mixture was transferred into a beaker. The catalyst was separated with a centrifuge. The reaction product was precipitated in a mixture of acetone and water (1:1). The product was filtered and dried in a vacuum drying chamber and analysed with HPLC. The reaction products are monomers.
Example 2: Inventive Example
(3) 70 g melamine, 100 g 1,4-butanediol and 1 g triruthenium dodecarbonyl were mixed in a beaker and filled into the autoclave. The autoclave was closed and the stirrer was turned on with 500 rpm. After flushing with helium, hydrogen was flushed through the autoclaved and then it was closed with atmospheric pressure of hydrogen inside. The reaction mixture was heated up to 250 C. and held at this temperature for 6 hours. After cooling down to room temperature and flushing with helium the autoclave was opened and the reaction mixture was transferred into a beaker. The reaction product was dissolved in 500 ml acetone-water (7:1). The catalyst was separated with a centrifuge and the solvent (water) was evaporated in a Rotavapor. The residue was dried in a vacuum drying chamber and analysed with HPLC. The reaction product was washed with acetone, filtered and analysed with HPLC. The solvent of the filtrate was evaporated with the Rotavapor and the residue was analysed by HPLC. The product has a yield of precondensate with minimum 2 triazine units of >90%. The product is water soluble.
(4) Tables 1 and 2 depict determined structures of the reaction according to Example 2. It is to be noted that the side chain formed from butanediol may also undergo a cyclization forming a pyrrolidin moiety. Table 1 depicts the monomeric structures wherein their percentage is below 10%. Table 2 depicts the structures of the present precondensate products comprising preferably 2-3 triazine.
(5) TABLE-US-00001 TABLE 1 Molecular Retention weight Time Structure (Examples) [g/mol] [min] 1 Triazine unit 1 Alcohol unit
(6) TABLE-US-00002 TABLE 2 Molecular Retention weight Time Structure (Examples) [g/mol] [min] 2 Triazine units 1 Alcohol unit
(7) HPLC-Method: Column: Purospher STAR RP-8e (5 m) LiChroCART 125-2 HPLC Cartridge Mobile Phase: A: Water (1 g ammonium formiate+20 l NH.sub.4OH Conc. (25%) per liter) B: Acetonitril Gradient:
(8) TABLE-US-00003 Time(min) % A % B 0 90 10 2 90 10 24 3 97 32 3 97 32.01 90 10 Temperature: 40 C.
Example 3: Inventive Example
(9) 70 g melamine, 100 g 1,4-butanediol and 1 g triiron dodecarbonyl were mixed in a beaker and filled into the autoclave. The autoclave was closed and the stirrer was turned on with 500 rpm. After flushing with helium, hydrogen was flushed through the autoclaved and then it was closed with atmospheric pressure of hydrogen inside. The reaction mixture was heated up to 250 C. and held at this temperature for 6 hours. After cooling down to room temperature and flushing with helium the autoclave was opened and the reaction mixture was transferred into a beaker. The reaction product was dissolved in 500 ml acetone-water (7:1). The catalyst was separated with a centrifuge and the solvent (water) was evaporated in a Rotavapor. The residue was dried in a vacuum drying chamber and analysed with HPLC. The reaction product was washed with acetone, filtered and analysed with HPLC. The solvent of the filtrate was evaporated with the Rotavapor and the residue was analysed by HPLC. The product is water soluble.
(10) Tables 3 and 4 depict determined structures of the reaction according to Example 3. It is to be noted that the side chain formed from butanediol may also undergo a cyclization forming a pyrrolidin moiety. Table 3 depicts the monomeric structures wherein their percentage is below 10%. Table 4 depicts the structures of the present precondensate products comprising preferably 2-3 triazine.
(11) TABLE-US-00004 TABLE 3 Molecular Retention weight Time Structure (Examples) [g/mol] [min] 1 Triazine unit 1 Alcohol unit
(12) TABLE-US-00005 TABLE 4 Molecular Retention weight Time Structure (Examples) [g/mol] [min] 2 Triazine units 1 Alcohol unit
(13) Hplc-Method: Column: Purospher STAR RP-8e (5 m) LiChroCART 125-2 HPLC Cartridge Mobile Phase: A: Water (1 g ammonium formiate+20 l NH.sub.4OH Conc. (25%) per liter) B: Acetonitril Gradient:
(14) TABLE-US-00006 Time(min) % A % B 0 90 10 2 90 10 24 3 97 32 3 97 32.01 90 10 Temperature: 40 C.